US6692621B1 - Apparatus for hydrogen production - Google Patents
Apparatus for hydrogen production Download PDFInfo
- Publication number
- US6692621B1 US6692621B1 US09/979,973 US97997302A US6692621B1 US 6692621 B1 US6692621 B1 US 6692621B1 US 97997302 A US97997302 A US 97997302A US 6692621 B1 US6692621 B1 US 6692621B1
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- US
- United States
- Prior art keywords
- electrolyte
- hydrogen
- water
- housing
- oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related, expires
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- the field of the invention is electrolytic hydrogen production.
- Hydrogen exhibits many advantages as an alternative energy source, including high energy density, and environmentally neutral combustion or recombination with oxygen. Furthermore, hydrogen can be generated from water in a relatively simple process (e g., water electrolysis), with almost no undesirable byproducts. However, despite the conceptually simple generation of hydrogen by water electrolysis, the energy efficiency of water electrolysis remains often problematic, and many approaches have been developed to improve the electrolytic generation of hydrogen.
- water electrolysis is powered or assisted by electricity generated in photovoltaic cells.
- photovoltaic cells are particularly attractive, because photovoltaic cells produce voltages and currents suitable for electro-dissociation of water in an environmentally neutral manner.
- industrial scale production of hydrogen supported by photovoltaic cells with current technology would require vast arrays of photovoltaic cells.
- large arrays of photovoltaic cells would incur a considerable cost.
- the electrolyte in a water electrolysis cell is heated to achieve improved conductivity. Improved conductivity of the electrolyte generally allows passing higher currents through the electrodes, and thereby increases hydrogen production per electrolysis cell.
- the energy cost to heat the electrolyte often reduces the overall efficiency of the electrolytic process.
- the use of a heated electrolyte frequently poses various problems due to the chemically aggressive character of some heated electrolytes.
- both photovoltaic and thermally assisted electrolysis typically produce hydrogen gas at or near atmospheric pressure. Consequently, when hydrogen needs to be stored or transported, additional energy must be spent to compress or liquefy the produced hydrogen gas.
- Smith discloses in U.S. Pat. No. 4,530,744 hydrogen electrolysis under pressure, in which water is pumped into an electrolyzer at an elevated pressure (typically 45 bar), resulting in a compressed hydrogen stream and a compressed oxygen stream. Smith's hydrogen stream is subsequently liquefied by cooling the hydrogen stream via expansion of the compressed oxygen stream.
- Smith's process requires a considerable amount of energy to compress the water, which is only partially recovered by expanding the oxygen stream for the cooling process.
- Smith's electrolyzer requires a pressure resistant configuration, demanding especially thick walls and gas tight joints due to the considerable pressure differences between the inside and the outside of the pressure electrolysis unit.
- the present invention is directed to an apparatus with a housing at least partially filled with an electrolyte, and a pair of electrodes (i.e., an anode and a cathode) disposed within the electrolyte to split the electrolyte into a first and a second product gas when a voltage is applied.
- a pair of electrodes i.e., an anode and a cathode
- Both electrodes are disposed in the electrolyte at a depth sufficient for a reduction in electrolyzing energy of greater or equal than 10%. It is generally preferred that the housing is disposed in, or part of, a deep well, or below the surface of a body of water.
- the electrolyte comprises water, preferably purified water, and even more preferably deionized water from a reverse osmosis unit. Consequently, a preferred first product gas is hydrogen and a preferred second product gas is oxygen.
- the depth at which the electrodes are disposed at is between 300 and 500 meters, and preferably between 500 and 1,000 meters, however depths greater than 1,000 meters are also contemplated.
- FIG. 1 is a schematic vertical cross sectional view of an electrolysis apparatus according to the inventive subject matter.
- An electrolysis system generally comprises a housing that is at least partially filled with an electrolyte.
- An anode and a cathode are disposed within the electrolyte and electrolytically disintegrate the electrolyte into at least a first product and a second product when a voltage is applied across the electrodes.
- Both anode and cathode are located in the electrolyte at a depth sufficient for a reduction in an electrolyzing energy of greater or equal than 10%.
- FIG. 1 An exemplary electrolysis system 10 is shown in FIG. 1 having a head portion 18 operationally coupled to a well casing 30 .
- the head portion 18 has a hydrogen discharge 12 , an oxygen discharge 14 , and a water feed path 20 is in fluid communication with the electrolyte reservoir 36 , which is defined by the well casing 30 .
- the oxygen discharge 14 is fluidly coupled to the oxygen conduit 38
- the hydrogen discharge 12 is fluidly coupled to the hydrogen conduit 40 .
- An electrolyzer 44 with a plurality of electrodes i.e., cathodes and anodes—not explicitly shown
- the electrolyzer 44 is electrically coupled to an AC/DC converter 52 , and may further be fluidly coupled to an atomizer 50 and a chemical collector 48 .
- At least part of the electrolysis system is in a location below a surface normal to an operator of the electrolysis system (e.g. below ground or below sea level).
- a predominant portion (i.e., more than 90%) of the height of the electrolysis system is below the ground, and particularly preferred locations include natural and man-made subterranean cavities such as a bore hole, a deep well, a mine-shaft, or a cavity formed by geological events (e.g., erosion or volcanic activity).
- contemplated electrolysis systems need not necessarily be limited to a subterranean location.
- alternative electrolysis systems may be partially or entirely located on the surface of a natural or man-made slanted structure, including a hill or mountainside.
- contemplated electrolysis systems may be partially or entirely immersed in a body of water, including a lake or an ocean.
- the housing may be a natural or man-made structure.
- the housing may be formed from a well casing, which forms an electrolyte reservoir.
- a well casing which forms an electrolyte reservoir.
- Dedicated well casings are especially desirable, where leakage of the electrolyte would otherwise pose a significant problem, or where leaching of minerals or other substances would be detrimental to the composition of the electrolyte.
- a well casing may prevent microbial growth in the electrolyte.
- an existing cavity may be covered with a sealant or other coating to form the housing.
- the housing is formed by the borehole and a well casing or coating may be omitted altogether.
- a housing is formed from multiple, cylindrical elements (e.g., fabricated from stainless steel) with a diameter sufficiently wide to accommodate the electrolyzer, the hydrogen conduit and the oxygen conduit, and it is even more preferred that the housing is gradually assembled above ground as the nascent housing is deployed below the ground.
- suitable, shapes include triangular, rectangular, polygonal and irregularly shaped configurations.
- suitable housings extend in their longest dimension at least 300 meters, more preferably at least between 300 and 500 meters, or more, including 500 to 1,000 meters and more.
- Appropriate diameters of the housing are typically between less than 1 meter and 15 meters, however, diameters larger than 15 meters are also contemplated.
- suitable diameters may be 15 to 50 meters in diameter and more.
- the electrolyte comprises predominantly water, preferably freshwater, which may or may not be pretreated.
- pretreated refers to a physical or chemical process that alters (typically reduces) the concentration of gases, ionic, particulate, organic or inorganic matter.
- filtered, ion-exchanged, irradiated, or ozonized water is considered pretreated under the scope of this definition, and a particularly preferred pretreatment of water comprises degassing, and reverse osmosis.
- contemplated electrolytes may include treated and untreated sea water, treated and untreated fresh water, or other treated and untreated aqueous solutions such as processing fluids from industrial plants, sewage, etc. Consequently, where the electrolyte is predominantly water, the first product gas evolving at the cathode is hydrogen, while the second product gas evolving at the anode is oxygen.
- anode and cathode need not be limited to a particular configuration or type.
- electrodes There are many electrode materials and configurations known in the art, all of which are contemplated for use in conjunction with the teachings presented herein, so long as contemplated electrodes are capable of electrolyzing water into hydrogen and oxygen, and have a configuration that withstands the hydrostatic pressure at the depth where the electrodes are disposed.
- the electrodes may be coated with, or entirely be fabricated from one or more noble metals or their alloys.
- the configuration of appropriate electrodes may vary considerably.
- one or both electrodes may be an integral part of the housing.
- the distance of the cathode and anode may vary between several millimeters and several centimeters, and more.
- the voltage applied across the electrodes will typically be a function of the electrolyte, the conductivity, the configuration of the electrodes, etc., and may therefore vary between 0.1V and 10V, and more.
- the electrode configuration includes a diaphragm
- the nature and configuration of the diaphragm is not limiting to the inventive concept.
- a polymeric or ceramic diaphragm may be employed.
- both the anode and the cathode are disposed within the electrolyte at a depth sufficient for a reduction in an electrolyzing energy of greater or equal than 10%.
- electrolyzing energy refers to the energy required to electrolytically split a compound (typically water) into two products (typically H 2 and O 2 ) at a pressure of no more than 1.1 bar (equivalent to about 1 meter depth in water).
- the reduction of electrolyzing energy is at least 10% when the electrodes are placed at a depth between 300 and 500 meters.
- alternative depths are also contemplated, including depths between 500 and 1,000 meters, and more than 1,000 meters.
- the hydrostatic pressure of the electrolyte provides at least in part the reduction in electrolyzing energy.
- submersible electrolysis systems are known in the art, all of the known submersible electrolysis systems submerge the container with the electrolyte together with the electrodes, thereby inherently imposing various practical limitations on size, amount of electrolyte delivered, etc.
- the electrolytic system according to the inventive subject matter only the electrodes are disposed at a great depth within a housing holding the electrolyte. It is not the housing itself, but only the electrodes within the housing that are submerged at a great depth.
- the product gas conduits are configured to withstand the internal pressure of the compressed product gases.
- conduits for compressed gases are numerous configurations known in the art, all of which are contemplated for use herein.
- the conduits are formed by nested cylindrical elements that can easily be assembled and disassembled (i.e., extended and shortened) on the surface while lowering or retrieving the conduits from the housing (see also FIG. 1 ).
- at least part of the anode and cathode are fluidly coupled to the hydrogen conduit and the oxygen conduit.
- the power delivered to the electrodes is preferably AC power, and where AC power is utilized to drive the electrolysis, an AC/DC converter is preferably in close proximity to the electrodes.
- Further additional elements functionally coupled to the electrodes may include an atomizer that would agitate the molecules of water, or possibly other solid or liquid catalysts utilized in the electrolysis process. Where chemical catalysts are concerned, a chemical collector may be provided as well.
- a refrigeration unit may be operationally coupled to the housing, wherein the refrigeration unit utilizes the expansion energy of the compressed second product gas to cool and/or liquefy the compressed first product gas.
- a particularly suitable refrigeration system for the production of liquefied hydrogen employing compressed hydrogen gas and compressed oxygen gas is described in U. S. Pat. No. 4,530,744 to Smith, incorporated by reference herein.
- the electrolysis system according to the inventive subject matter may be operationally coupled to a deep well reverse osmosis unit that feeds purified water to the electrodes.
- a typical deep well reverse osmosis unit is described, for example, in U.S. Pat. No. 5,914,014 to Chancellor.
- the coupling may further, comprise an electrolyte make up system in which acid, base, or salts are admixed to the purified water.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
Claims (11)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/979,973 US6692621B1 (en) | 1999-07-28 | 2000-07-27 | Apparatus for hydrogen production |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US14631199P | 1999-07-28 | 1999-07-28 | |
US09/979,973 US6692621B1 (en) | 1999-07-28 | 2000-07-27 | Apparatus for hydrogen production |
PCT/US2000/020537 WO2001009408A1 (en) | 1999-07-28 | 2000-07-27 | Apparatus for hydrogen production |
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US6692621B1 true US6692621B1 (en) | 2004-02-17 |
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US09/979,973 Expired - Fee Related US6692621B1 (en) | 1999-07-28 | 2000-07-27 | Apparatus for hydrogen production |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8168048B1 (en) * | 2006-02-03 | 2012-05-01 | M&R Consulting Services, Inc. | Carbon dioxide generation and dispensing device and method of production |
US20120222953A1 (en) * | 2011-03-02 | 2012-09-06 | Anderson Kenneth W | Systems and Methods for Producing Pressurized Gases from Polar Molecular Liquids at Depth |
US20150121869A1 (en) * | 2004-11-09 | 2015-05-07 | Mcalister Technologies, Llc | Sustainable economic development through integrated production of renewable energy, materials resources, and nutrient regimes |
WO2015163932A1 (en) * | 2014-04-21 | 2015-10-29 | Bower Joseph P | System and method for the manufacture, storage and transportation of hydrogen and oxygen gas |
US9315397B2 (en) | 2012-12-10 | 2016-04-19 | Samuel Sivret | Blue power generation system |
JP2019065367A (en) * | 2017-10-04 | 2019-04-25 | 株式会社豊田中央研究所 | Light energy utilization device |
CN110699699A (en) * | 2018-07-09 | 2020-01-17 | 丰田自动车株式会社 | Hydrogen generation system and method for generating hydrogen |
CN110820007A (en) * | 2019-11-14 | 2020-02-21 | 深圳大学 | PBI proton exchange membrane electrolysis module and seawater electrolysis hydrogen production device |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US721068A (en) | 1902-04-22 | 1903-02-17 | Arthur Coppell | Apparatus for decomposing water by electrolysis. |
US1398658A (en) | 1919-01-13 | 1921-11-29 | Frank S Vincent | Process for extracting gases from liquids |
US3647672A (en) | 1967-11-13 | 1972-03-07 | Nautchno Izsledovatelski Inst | Electrode with aerolifting and gas-separation effects for electrolysis of solutions of electrolytes |
US4490232A (en) | 1981-10-29 | 1984-12-25 | The Laitram Corporation | Wave-powered electrolysis of water |
US4564458A (en) * | 1983-11-10 | 1986-01-14 | Burleson James C | Method and apparatus for disposal of a broad spectrum of waste featuring oxidation of waste |
US5167786A (en) * | 1991-01-25 | 1992-12-01 | Eberle William J | Wave-power collection apparatus |
US5690797A (en) * | 1995-01-18 | 1997-11-25 | Mitsubishi Corporation | Hydrogen and oxygen gas generating system |
US5711865A (en) * | 1993-03-15 | 1998-01-27 | Rhyddings Pty Ltd | Electrolytic gas producer method and apparatus |
-
2000
- 2000-07-27 US US09/979,973 patent/US6692621B1/en not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US721068A (en) | 1902-04-22 | 1903-02-17 | Arthur Coppell | Apparatus for decomposing water by electrolysis. |
US1398658A (en) | 1919-01-13 | 1921-11-29 | Frank S Vincent | Process for extracting gases from liquids |
US3647672A (en) | 1967-11-13 | 1972-03-07 | Nautchno Izsledovatelski Inst | Electrode with aerolifting and gas-separation effects for electrolysis of solutions of electrolytes |
US4490232A (en) | 1981-10-29 | 1984-12-25 | The Laitram Corporation | Wave-powered electrolysis of water |
US4564458A (en) * | 1983-11-10 | 1986-01-14 | Burleson James C | Method and apparatus for disposal of a broad spectrum of waste featuring oxidation of waste |
US5167786A (en) * | 1991-01-25 | 1992-12-01 | Eberle William J | Wave-power collection apparatus |
US5711865A (en) * | 1993-03-15 | 1998-01-27 | Rhyddings Pty Ltd | Electrolytic gas producer method and apparatus |
US5690797A (en) * | 1995-01-18 | 1997-11-25 | Mitsubishi Corporation | Hydrogen and oxygen gas generating system |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150121869A1 (en) * | 2004-11-09 | 2015-05-07 | Mcalister Technologies, Llc | Sustainable economic development through integrated production of renewable energy, materials resources, and nutrient regimes |
US8168048B1 (en) * | 2006-02-03 | 2012-05-01 | M&R Consulting Services, Inc. | Carbon dioxide generation and dispensing device and method of production |
US20120222953A1 (en) * | 2011-03-02 | 2012-09-06 | Anderson Kenneth W | Systems and Methods for Producing Pressurized Gases from Polar Molecular Liquids at Depth |
US9315397B2 (en) | 2012-12-10 | 2016-04-19 | Samuel Sivret | Blue power generation system |
WO2015163932A1 (en) * | 2014-04-21 | 2015-10-29 | Bower Joseph P | System and method for the manufacture, storage and transportation of hydrogen and oxygen gas |
US9273402B2 (en) * | 2014-04-21 | 2016-03-01 | Joseph P. Bower | System and method for the manufacture, storage and transportation of hydrogen and oxygen gas |
JP2019065367A (en) * | 2017-10-04 | 2019-04-25 | 株式会社豊田中央研究所 | Light energy utilization device |
CN110699699A (en) * | 2018-07-09 | 2020-01-17 | 丰田自动车株式会社 | Hydrogen generation system and method for generating hydrogen |
CN110820007A (en) * | 2019-11-14 | 2020-02-21 | 深圳大学 | PBI proton exchange membrane electrolysis module and seawater electrolysis hydrogen production device |
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